Process for the preparation of 2-(hydroxyhydrocarbyl)acrylates

ABSTRACT

A process for preparing Alpha , Beta -ethylenically unsaturated compounds of the formula WHEREIN R is a hydrocarbon radical which comprises reacting an Alpha , Beta -ethylenically unsaturated compound of the formula

United States Patent Morita et a1.

[54] PROCESS FOR THE PREPARATION OF 2-(HYDROXYHYDROCARBYL)ACRY- LATES [72] inventors: Ken-Ichl Morita; Zennosuke Suzuki; Hiromitsu Hirose, all of Kamakura-shi, Japan Dec. 24, 1965 Japan ..40/79319 Dec. 25, 1965 Japan ..40/79595 March 29, 1966 Japan ..4l/l8933 [52] U.S. Cl. ..260/468 R, 260/88.7, 260/89.5, 260/464, 260/465.6, 260/47 R, 260/473 A, 260/479 R,'260/484 R [51 Int. Cl. .C07c 69/66, C07c 69/76, C08f 9/74 [58] Field of Search ..260/465 F, 465 D, 468 R, 473 A, 260/484 R, 479 R, 471 R [56] References Cited UNITED STATES PATENTS 3,361,785 1/1968 McClure ..260/465 Primary Examiner-Joseph Rebold Assistant Examiner-Dolph H. Torrence Anarney--Sherman and Shalloway 51- July 18, 1972 ABSTRACT A process for preparing .mfi-ethylenically unsaturated compounds of the formula cu iae-4:00 n

R()ll()ll wherein R is a hydrocarbon radical which comprises reacting an a,B-ethylenically unsaturated compound of the formula CH, CH-COOR wherein R is as defined above with an aldehyde of the formula RCHO

wherein R is as defined above in the process of a catalyst selected from compounds of the formula wherein R, R and R each are hydrocarbyl groups having up to 12 carbon atoms selected from the group consisting of alkyl groups, cycloalkyl groups and aryl groups with the proviso that at least one of the R, R and R is an alkyl or cycloalkyl group, and compounds having the formula R-P R' wherein R is a hydrocarbyl group having up to 12 carbon atoms selected from the group consisting of alkyl groups and cycloalkyl groups and R is a divalent hydrocarbyl group selected from the group consisting of alkylene and alkenylene groups.

1 Claim, No Drawings PROCESS FOR THE PREPARATION OF 2- (HYDROXYHYDROCARBYIJACRYLATES This application is a division of co-pending application Ser. No. 602,495 filed Dec. 19, 1966, now US. Pat. No. 3,499,024.

This invention relates to a process for preparing alpha, betaethylenically unsaturated compounds comprehending new compounds, and also new acrylonitrile derivatives.

Acrylonitrile, acrylic esters and the derivatives thereof have been widely used in the past either as monomers of various resins or as material for the manufacture of organic chemicals. The acrylonitrile derivatives having, for example, the hydroxyhydrocarbyl radical (of more than 1 carbon atom) in the 2- position have however not been known at all prior to this invention.

An object of this invention is to provide valuable alpha, beta-ethylenically unsaturated compounds which possess per se great polymerization activity and are useful as monomers for the preparation of such as adhesives, paints and resins for molding, as well as are valuable as intermediates for the manufacture of various organic chemicals.

Another object is to provide a new process for preparing alpha, beta-ethylenically unsaturated compounds, whereby these compounds can be prepared with a simple process from low cost materials.

A further specific object of this invention is to provide new acrylonitrile derivatives which have the hydroxyhydrocarbyl radical in the 2-position.

wherein X is CN or COOR radical and R is a hydrocarbon radical of one to 12 carbon atoms.

R in the above formula is preferably either an alkyl radical of not more than 12 carbon atoms, and particularly not more than eight, a cycloalkyl radical of five to 12 carbon atoms, and particularly five to eight, an aryl radical of six to 12 carbon atoms, an aralkyl radical of seven to 12 carbon atoms, or an alkenyl radical of three to eight carbon atoms. The foregoing radicals, when specifically illustrated, include the straight chain or branched alkyl radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl and dodecyl; the cycloalkyl radicals such as cyclopentyl, cyclohexyl, cyclohep' tyl, cyclooctyl and cyclodecyl; the aryl radicals such as phenyl,naphthyl and tolyl; the aralkyl radicals such as benzyl; and the alkenyl radicals such as allyl. Of these hydrocarbon radicals, the aryl and aralkyl radicals may be ones whose nucleus is substituted by a substituent such as halogens, or the nitro, lower alkoxy or lower carboalkoxy radical.

Of the compounds comprehended by the aforesaid formula I, the acrylonitrile derivatives of the following formula are new compounds unreported as yet in literature.

wherein Y is halogen, hydrogen, or nitro, lower alkyl or lower alkoxycarbonyl radical, and n is an integer l to 5.

According to this invention, the aforesaid alpha, betaethylenically unsaturated compounds of formula I are obtained by a new process which comprises reacting a compound of the formula CH Cl-l-X, wherein X is a CN or COOR radical and R is a hydrocarbon radical of one to 12 carbon atoms, with an aldehyde of two to 13 carbon atoms in the presence of a catalytic amount of a tertiary phosphine.

The aldehydes used in this invention having the formula RCHO, wherein R has the meaning hereinbefore defined, include, e.g., acetaldehyde, propionaldehyde, n-butyraldehyde, iso-butyraldehyde, n-valeraldehyde, iso-valeraldehyde, ncaproaldehyde, n-heptanal, n-octanal, n-dodecanal, benzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, mtolualdehyde, alpha-phenylacetaldehyde, cyclohexylaldehyde and cyclooctylaldehyde The acrylic esters, one of the starting materials of this invention, are exemplified by methyl acrylate, ethyl acrylate, nor isopropyl acrylate, n-, iso, sec., or tert. butyl acrylate, hexyl acrylate, octyl acrylate, cyclohexyl acrylate, alkyl acrylate and phenyl acrylate.

The tertiary phosphines to be used as catalyst in the invention process are preferably tertiary phosphines which have at least one aliphatic radical attached to the phosphorus atom from the standpoint of their activity. Such tertiary phosphines are represented by either the formula:

wherein R, R and R are either an aliphatic or aromatic radical with the proviso that at least one of them is a saturated aliphatic radical; or the formula wherein R is an aliphatic radical and R is a divalent hydrocarbon radical. Examples of the foregoing tertiary phosphines include trimethylphosphine, triethylphosphine, tributylphosphine, trihexylphosphine, tricyclooctylphosphine, diethylcyclohexylphosphine, diphenyl4- hydroxybutylphosphine, phenyldibutylphosphine, tribornylphosphine, lphenyl-3-methyl-3-phospholene,

C H -P and C zHgP It is preferable that each of the hydrocarbyl radicals attached to phosphorus constituting the tertiary phosphine should have not more than 12, particularly not more than eight, carbon atoms.

While the foregoing tertiary phosphines are used in a socalled catalytic amount, the amount used varies depending upon the tertiary phosphine compound used. Generally, their use in an amount of about 0.000l-0.l mole, and preferably 0.00l-0.0l mole, of the acrylonitrile or acrylic ester will do. In practicing the invention process, the use of the aldehydes in an amount of 0.5-5 moles, and particularly 0.7-3 moles, is to be preferred. A reaction temperature in a range of 20 to 250C, and particularly 30 to 180C, is desirable. Although the presence of a reaction medium is not necessarily required, the use of an inert organic solvent is desirable. Inert organic solvents of this sort include such as acetonitrile, cyclohexane, tert. butyl alcohol, dioxane, tetrahydrofuran, diethylene glycol, dimethyl ether, dimethylformamide, toluene pyridine and benzene.

According to this invention, it was found that if a tertiary amine was added to the reaction system when using acrylonitrile as a starting material the reaction would proceed much more favorably even when the aforesaid tertiary phosphine is used in a small amount. Suitable tertiary amines are those whose basic tenacity PKa at 25C. is at least 5. The foregoing PKa is defined by the following expression:

wherein the R 6N is an amine, the several R6 of which represent a hydrocarbon radical.

As suitable tertiary amines can be used the aliphatic tertiary amines, aromatic tertiary amines, heterocyclic tertiary amines and mixed aliphatic-aromatic amines. Examples of these tertiary amines include such compounds as trimethylamine, triethylamine, tributylamine, N-methylpyrrolidine, N-ethylpyrrolidine; N-methylmorpholine, N-bicyclo [2,2,2] octylpyrrolidine, dimethylaniline, pyridine and quinoline. The tertiary amine is preferably used in an amount of 0.01 to 10 moles per each mole of the material acrylonitrile.

A polymerization inhibitor can also be added to the reaction system in practicing the invention process. Suitable polymerization inhibitors are hydroquinone and tert.-butylpyrocatechol.

The atmosphere of the reaction system should preferably be either a nonoxidizing atmosphere such as of nitrogen or argon or reduced pressure, it being desirable to avoid the presence of air, as far as possible.

Thus, a new acrylonitrile derivative having the alphahydroxyhydrocarbon radical in the 2-position can be obtained accordingto this invention. It was found that the new acrylonitrile derivative of this invention had great polymerization activity. Hence, it could be used alone or by being combined into a composition with other comonomers to become the starting material for the preparation of adhesives, paints, resins for molding use or fiber-forming polymers. For example, the new acrylonitrile derivative of this invention can be copolymerized with acrylonitrile to improve the dyeability and absorption property of acrylonitrile fibers. Further, since the new acrylonitrile derivative of this invention possesses the two functional radicals of nitrile and hydroxyl radicals, the synthesis of a wide variety of compounds is possible using this acrylonitrile derivative.

A process for preparing an acrylic acid derivative having the alpha-hydroxyhydrocarbon radical in the 2-position and having also a free carboxylic acid radical by using acetylene derivatives as the starting material has been known prior to this invention (German Patent No. 855,110)

This process is very difficult however, and there were many drawbacks in its commercial practice. In addition, the yield was also generally low.

In contradistinction, according to the process of this invention, it is possible to obtain in relatively good yield a wide variety of acrylic ester derivatives having the alpha-hydroxyhydrocarbon radical in the 2-position by using as the starting material the relatively low cost acrylic esters and reacting them with any of the optional aldehydes in the presence of a tertiary phosphine. The acrylic ester derivatives according to this invention can be used as starting materials for the preparation of paints, adhesives and resins for molding use.

For a further understanding of this invention the following examples are given, it being understood that these examples are in illustration and not in limitation of the invention is no sense whatsoever.

EXAMPLE 1 5.7 grams of commercial special grade acrylonitrile and 4.4 grams of n-butylaldehyde were dissolved in 30 ml of purified dioxane. While boiling this solution under reflux in a stream of nitrogen, 0.6 gram of trichlorohexylphosphine in I ml of dioxane was added dropwise to the solution over a period of 20 minutes. After boiling the reaction mixture for 16 hours under reflux, the solvent was distilled 05 to yield after vacuum distillation of the residue 6.63 grams of 2-( l-dihydroxybutyl) acrylonitrile having a boiling point of 76 to 77C. (0.5 mm Hg). This corresponded to a conversion rate of 67 percent and a yield of 85 percent.

Infrared Spectrum of the Product:

229 cm (CN): 1,623 cm (6 0 double bond) Nuclear Magnetic Resonance Spectrum of the Product:

3.98, 4.30 r (terminal double bond) triplet centered at 5.78 r (J 6 C.P.S.) (hydrogen on a carbon atom bearing hydroxyl group) Ultimate Analysis of the Product:

C H N Molecular weight Thcoreticalvalue 67.17 8.86 11.19 125 Analytical Measuredvaluc 67.44 8.97 ll.36 I22 EXAMPLEZ 1 gram of tricyclohexylphosphine was dissolved in 60 ml of dioxane, after which this solution was boiling under reflux in a stream of nitrogen. To this solution were then added dropwise over a period of 6 hours 22 grams of acrylonitrile and 34 grams of acetaldehyde dissolved in 30 ml of dioxane. After completion of the dropwise addition of the latter solution, the reaction mixture was boiled under reflux for a further 5 hours. The solvent was then distilled off from the reaction mixture, a small amount of pyrogallol was added thereto, followed by vacuum distillation of the product, whereupon was obtained 2-( l-hydroxyethyl) acrylonitrile having a boiling point of 77 to 78C. (7 mm Hg) at a conversion rate of 25 percent and a yield of 88 percent, based on the acrylonitrile.

Infrared Spectrum of the Product:

2,229 cm (CN) 1,623 cm (0 c double bond) Nuclear Magnetic Resonance Spectrum of the Product:

9.98, 4.05 1' (terminal double bond) triplet centered at 5.58 1' (J 6.5 C.P.S.) (hydrogen on a carbon atom bearing hydroxy group).

C H N Molecular weight Theoretical value 61.83 7.36 l4.48 97 Analytical measured value 6l.48 7.24 14.42 I00 EXAMPLE 3 5.3 grams of acrylonitrile and l 1.6 grams of propionaldehyde were dissolved in 20 ml of dioxane. While boiling this solution under reflux in a stream of nitrogen, 0.3 gram of tricyclohexylphosphine in 10 ml of dioxane was added dropwise to the solution over a period of 15 minutes. After boiling the reaction mixture for 12 hours under reflux, the solvent was distilled off and the residue was subjected to vacuum distillation, whereupon was obtained 2-( l-hydroxypropyl) acrylonitrile having a boiling point of 60 to 61C. (0.4 mm Hg), at a conversion rate of 35 percent and a yield of 90 percent, based on the acrylonitrile.

Infrared Spectrum of the product:

2,229 cm (CN): 1,623 cm (0 c) Nuclear Magnetic Resonance Spectrum of the Product:

4.02 1- (terminal double bond) triplet centered at 5.86 'r (J 6.5 C.P.S) (hydrogen on a carbon bearing hydroxyl group) EXAMPLE 4 C H N Molecular weight Theoretical value 75.45 5.70 8.80 157 Analytical measured value 75.88 5.76 8.93 148 EXAMPLE 5 A mixture of grams of acrylonitrile, 30 grams of benzaldehyde and 2 grams of diphenyl-4-hydroxybutylphosphine was stirred continuously for 20 hours in a stream of nitrogen at room temperature. When the product was treated in customary manner, 4.5 grams of Z-(aIpha-hydroxybenzyl) acrylonitrile having a boiling point of 120 to 130C. (0.2 mm Hg) were obtained.

EXAMPLE 6 EXAMPLE 7 10.8 grams of commercial special grade acrylonitrile and 13.2 grams of acetaldehyde were dissolved in 20 cc of triethylamine and then, after adding 0.25 gram of tricyclohexylphosphine, the temperature of the mixture was immediately raised to 110C., at which temperature stirring of the mixture was carried out for 1 hour. The triethylamine and the unreacted acrylonitrile and. acetaldehyde were recovered by rectification, followed by obtaining 5.8 grams of 2-( l-hydroxyethyl) acrylonitrile.

EXAMPLE 8 13.3 grams of acrylonitrile and 14.5 grams of propionaldehyde were dissolved in a mixture of 20 ml of pyridine and ml of dioxane, to which was then added 0.45 grams of tricyclohexylphosphine, after which the mixture was stirred for 18 hours at 120C. After recovering the acrylonitrile and propionaldehyde by means of rectification, 8.7 grams of 2-(1- hydroxypropyl) acrylonitrile were obtained.

EXAMPLE 9 10 cc of acrylonitrile and 18 cc of propionaldehyde were dissolved in 40 cc of pyridine, following which 0.3 gram of triethylphosphine was added to the solution which was then stirred for 3 hours at 120C. After recovering the pyridine, acrylonitrile and propionaldehyde by means of rectification, 5.2 grams of 2-( l-hydroxypropyl) acrylonitrile were obtained.

arm!

EXAMPLE 10 13.3 grams of acrylonitrile and 18 grams of butylaldehyde were dissolved in a mixture of 20 cc of pyridine and 15 cc of dioxane. After adding 0.47 gram of tricyclohexylphosphine to the mixture, the temperature thereof was raised to 120C. at which temperature the mixture was maintained for 18 hours. After recovering the solvent and unreacted acrylonitrile and butylaldehyde, 8.5 grams of 2-(l-hydroxybutyl) acrylonitrile were obtained.

EXAMPLE 1 1 8 cc of acrylonitrile and 10 cc of butylaldehyde were mixed with 25 cc of N-methylpyrrolidine, after which 0.25 gram of tributylphosphine was added to the mixture, which was then stirred for 20 hours at 115C. The acrylonitrile and butylaldehyde were recovered by rectification, and further 5.5 grams of 2-( l-hydroxybutyl) acrylonitrile were obtained.

EXAMPLE 12 9.3 grams of commercial first grade methyl acrylate, 14.5 grams of butylaldehyde and 0.5 gram of tricyclohexylphosphine were dissolved in 30 ml of purified dioxane, following which the mixture was boiled under reflux for 15 hours in a stream of nitrogen. The solvent was then distilled off and the residue was subjected to vacuum distillation to obtain methyl 2-( l-hydroxybutyl) acrylate at a conversion rate of 70 percent and a yield of 83 percent, based on the methyl acrylate.

Infrared Spectrum of the Product:

1,722 cm (ester carbonyl) 1,635 cm (0 0) Nuclear Magnetic Resonance Spectrum of the Product:

3.98, 4.02 1- (terminal double bond) triplet centered at 5.79 1- (J 6 C.P.S.) (hydrogen on a carbon atom bearing hydroxyl group) Ultimate Analysis of the Product:

0.8 gram of tricyclohexylphosphine was dissolved in 40 m1 of dioxane, and the solution was boiled under reflux in a stream of nitrogen. To this were then added dropwise over a period of 6 hours 25.8 grams of methyl acrylate and 26.4 grams of acetaldehyde in solution in 30 ml of dioxane. After driving off the excess acetaldehyde and raising the boiling point, boiling under reflux was carried out for 3 more hours. When the solvent was distilled off from the reaction mixture, a small amount of pyrogallol was added thereto and the product was subjected to vacuum distillation, 6.2 grams of methyl 2- (l-hydroxyethyl) acrylate having a boiling point of 79 80C. (9 mm Hg) were obtained.

Infrared Spectrum of the Product:

17 19 cm (ester carbonyl) Nuclear Magnetic Resonance Spectrum of the Product:

3.72 1- (doublet J= 1.3 C.P.S.)

4.03 1 (triplet J= 1.3 C.P.S.)

5.35 1- (quartett J 6 C.P.S.)

Ultimate Analysis of the Product:

EXAMPLE 14 Except that ethyl acrylate was used insteaf of methyl acrylate, the experiment was otherwise carried out as in Example 13 to obtain ethyl 2-( l-hydroxyethyl) acrylate at a conversion rate of 25 percent and a yield of 89 percent.

EXAMPLE 15 8.6 grams of methyl acrylate and 12 grams of propionaldehyde were dissolved in 30 ml of dioxane and then while boiling this solution under reflux in a stream of nitrogen, 0.4 gram of tricyclohexylphosphine in 10 ml of dioxane was added dropwise to the solution over a 20-minute period. After boiling the reaction mixture under reflux for 15 hours, the solvent was distilled off and the residue was subjected to vacuum distillation, whereupon methyl 2-(1-hydr0xypropyl) acrylate having a boiling point of 55 to 56C. (2 mm Hg) was obtained at a conversion rate of 32 percent and a yield of 85 percent, based on the methyl acrylate.

EXAMPLE 16 A mixture of 8.8 grams of ethyl acrylate, 7.2 grams of butylaldehyde and 1.2 grams of diphenyl-4-hydroxybutylphosphine was boiled under reflux for 10 hours under a stream of nitrogen. When the product was treated in customary manner, 3.5 grams of ethyl 2-( l-hydroxybutyl) acrylate having a boiling point 70 to 71C. (0.3 mm Hg) were obtained.

EXAMPLE 17 A mixture of 16 grams of methyl acrylate, 30 grams of benzaldehyde and 2 grams of diphenyl-4-hydroxybutylphosphin'e was stirred continuously for 20 hours at 30 to 35C. in a stream of nitrogen. When the product was distilled, 6.2 grams of methyl 2-(alpha-hydroxybenzyl) acrylate having a boiling point of 103 to 105 C. (0.1 mm Hg) were obtained.

EXAMPLE 18 0.53 gram of tricyclohexylphosphine-carbon disulfide addition product was dissolved in 10 cc of ethanol in a stream of nitrogen, after which the ethanol was slowly distilled off. After the formation of the distillate had stopped, 15 cc of dioxane was added and the mixture was boiled to distill ofi 5 cc of the dioxane. After cooling the mixture to C., 11 grams of acrylonitrile, 12 grams of n-octanal, 10 ml. of dioxane and 20 ml of pyridine were added thereto, following which the mixture was heated for 12 hours at 120C. in a sealed tube. The solvent was then driven under reduced pressure, following which the residue was purified by means of alumina column chromatography. 2-( l-hydroxyoctyl) acrylonitrile having a boiling point of 107 to 108C. (0.7 mm Hg) was obtained at a conversion rate of 45 percent and a yield of 52 percent.

if, instead of n-octanal, an equimolar quantity of cyclohexyl-aldehyde, cyclo-octylaldehyde, n-caproaldehyde, p-tolualdehyde and alpha-phenylacetaldehyde are used, 2-(alphahydroxycyclohexylmethyl) acrylonitrile (b.p. 105 to 106C, 1 mm Hg), 2-(alpha-hydroxycyclooctylmethyl) acrylonitrile (b.p. 60 to 61C., 1 X mm Hg), 2-(l-hydroxycapryl) acrylonitrile (b.p. 70C., 1 X 10" mm Hg), Z-(aIpha-hydroxypmethylbenzyl) acrylonitrile (b.p. 128 to 130C., 0.2 mm Hg) and 2-(alpha-hydroxy-beta-phenylethyl) acrylonitrile (b.p. 157 to 160C., 1 X 10 mm Hg) are obtained respectively.

EXAMPLE 19 6 grams of p-chlorobenzaldehyde and 5.3 grams of acrylonitrile were dissolved in a mixture of 90 ml of dioxane and ml of pyridine. To this mixture was then added a solution of 0.6 gram of tricyclohexylphosphine in ml of dioxane, after which the mixture was held at 30C. in a sealed tube for 10 hours. After opening the tube, 0.3 ml of concentrated hydrochloric acid was added to the content, the solvent was distilled off and thereafter the residue was subjected to vacuum distillation, whereupon were obtained 6.5 grams of 2- (alpha-hydroxy-p-benzyl) acrylonitrile having a boiling point of 140 to 150C. (0.2 mm Hg).

By following the hereinabove described procedure, 5 grams of 2-(alpha-hydroxy-p-methylbenzyl) acrylonitrile having a boiling point of 128 to 130C. (0.2 mm Hg) were obtained from 6 grams of p-tolualdehyde and 5.3 grams of acrylonitrile. Similarly, 6.2 grams of 2-alpha-hydroxy-m-nitrobenzyl) acrylonitrile having a boiling point of 160 to 165C. (1 X 10 mm Hg) were obtained from 6 grams of m-nitrobenzaldehyde and 5 grams of acrylonitrile. Further, 7.2 grams of 2-(alphahydroxy-p-carbomethoxybenzyl) acrylonitrile having a boiling point of 150 to 155C. (1 X 10'' mm Hg) were obtained from 6.8 grams of p-carbomethoxybenzaldehyde and 5.3 grams of acrylonitrile.

EXAMPLE 20 Three grams of n-octyl acrylate and 1.4 grams of acetaldehyde were dissolved in 30 ml of dioxane followed by addition thereto of 0.035 gram of tricyclohexylphosphine. This mixture was then reacted in a sealed tube for 2 hours at 120 to 130C. When the reaction product was subjected to a purification treatment according to customary procedures, 1.5 grams of octyl 2-(1-hydroxyethyl) acrylate having boiling point of 120 to 121C. (7 mm Hg) was obtained.

When the reaction was carried out as hereinabove described except that n-butyl acrylate and benzyl acrylate were used instead of octyl acrylate, n-butyl 2-( l-hydroxyethyl) acrylate (b.p. 70 to 71C., 4 mm Hg) and benzyl 2-(1- hydroxyethyl) acrylate (b.p. 135 to 137C., 4 mm Hg) were obtained respectively.

EXAMPLE 21 A solution of 0.8 gram of tricyclohexylphosphine in m1 of dioxane was added to a solution of 5.7 grams of allyl acrylate and 3.6 grams of n-butylaldehyde in 20 ml of dioxane, following which the mixture was boiled under reflux for 3 hours. When 0.5 grams of acetic acid was added to the mixture which was the subjected to distillation, 3.1 grams of allyl 2-(1- hydroxy-nbutyl) acrylate having a boiling point of 77C. (1 mm Hg) were obtained.

EXAMPLE 22 To a solution of 7 grams of benzaldehyde and 7 grams of acrylonitrile in m1 of dioxane was added a solution of 20 ml of pyridine and 2 millimoles of a below-indicated tertiary phosphine in 20 ml of dioxane, following which the mixture was allowed to stand for 6 hours at 30C. in a sealed tube. Thereafter, a small quantity of concerntrated HCl was added to the contents and solvent was distilled off. This was followed by diluting the reaction product with ether, washing with water and drying, followed by subjecting the reaction product to distillation. The yield was as follows:

Yield Tertiary phosphine tricyclohexylphosphine tricyclopentylphosphine tribornylphosphine tri-n-octylphosphine tri-n-butylphosphine triisopropylphosphine phenyl diethylphosphine EXAMPLE 23 2.65 grams of acrylonitrile and 3.24 grams of n-butylaldehyde were dissolved in 15 ml of a solvent indicated below. After adding a l-ml dioxane solution of 0.19 gram of tricyclohexylphosphine, the reaction was carried out for 15 hours at to C. After cooling the reaction mixture, a small quantity of acetic acid was added, followed by distilling off the solvent. The reaction product was then subjected to comprises reacting an alpha, beta-ethylenically unsaturated distillation to isolate 2-(l-hydroxybutyl) acrylonitrile. The compound having the formula yield was as follows:

CH Cl-l-COOR Yield 5 wherein R has the same meaning as defined above, with an 8 aldehyde having the formula Zil3e l? t rinbutylalcohol 0.9 RCHO dioxane 2,7 wherein R has the same meaning as defined above, at a tem- "f y rofuran 2.7 10 perature of from 20 to 250C. in the presence of a gfil lggqiglggl lflqlll fil catalyst in an amount of 0.0001 to 0.1 mole per mole of m 0 e said alpha, beta-ethylenically unsaturated compound, pyridine said catalyst being selected from the group consisting of benzene 1.9 compounds having the formula What is claimed is RRR? l. A process for preparing alpha, beta-ethylenically unsatuwherein R, R and R each are hydrocarbyl groups having rated compounds having the formula up to 12 carbon atoms selected from the group consisting of alkyl groups, cycloalkyl groups and aryl groups with CHFC-COOR the proviso that at least one of R, R and R is an alkyl or eycloalkyl group, ,V V and compounds having the formula R is a hydrocarbon radical selected from the group consisting of alkyl groups having up to 12 carbon atoms, cycloalkyl groups having five to 12 carbon atoms, aryl groups R"PR wherein R is a hydrocarbyl group having up to 12 carbon having six to 12 carbon atoms, aralkyl groups having three to eight carbon atoms and said aryl and aralkyl groups further having a substituent selected from the atoms selected from the group consisting of alkyl groups and cycloalkyl groups and R is a divalent hydrocarbyl group selected from the group consisting of alkylene and group consisting of a chloro, nitro, lower alkoxy and alkenylene gmups' lower carboalkoxy groups, which 

